Installing charge in diphosphine borate end-group ligands Rayni P. Noriega, Devon Facchinato, Marcus W. Drover Department of Chemistry, Western University, Ontario, Canada Diphosphine ligands have been explored extensively by the Drover group as scaffolds for Lewis-acidic secondary coordination spheres (SCSs). Their coordination has been explored with multiple metals 1,2,3 and their reactivity in hydride transfer 1 , transmetalation 3 , oxidative addition 4 , and more, has been studied. The SCS allows for the stabilization of small molecules by taking advantage of non-covalent interactions. 5 In the realm of reactivity, electrostatic forces influence the likelihood of two atoms orienting themselves correctly, and closely enough, to react and form a product. 6 By charging the substrate or the metal complex, one can take advantage of electrostatic forces to induce difficult chemical transformations. In previous reports, the interaction between charged transition metal catalysts and substrates has been used to control site-selectivity. 7 The use of opposing charges is a simple, but effective, means to cause attraction between two molecules that change reactivity. This work expands on the ligand design toolbox: unsaturated diphosphine ligand starting materials have been used to construct novel charged ligand scaffolds, by installaling anionic borate fragments into the SCS of nickel complexes. These charged groups are investigated in their role to increase the rate of oxidative addition, through opposite charge attraction, with aromatic halides. References 1. Zurakowski, J.A.; Austen, B.J.H.; Drover, M.W. Organometallics. 2021 , 40 , 2450. 2. Drover, M.W.; Bowes, E.G.;Dufour, M.C.;Lesperance-Nantau, L.A. Dalton Trans . 2020 , 49 , 16312. 3. Demchuk, M. J.;Zurakowski, J.A.;Austen, B.J.H.; Nelson, D.J.;Drover, M.W. Chem. Commun . 2022 , 58 ,68. 4. Zurakowski, J.A.;Dufour, M.C.;Austen, B.J.H.; Spasyuk, D.M.; Nelson, D.J.;Drover, M.W. Chem. Eur. J . 2021 , 27 ,16021. 5. Drover, M.W. Chem. Soc. Rev . 2022 , 51 , 1861 6. .Jacobsen, E. N.; Brak, K. Angew.Chem.Int. 2013 , 52 , 534. 7. Gillespie, J. E.; Fanourakis, A.; Phipps, R. J. J. Am. Chem. Soc. 2022 , 144 , 18195.
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